Method and device for disposing of pollutants in hydrogen production

Abstract

The invention relates to a method and a device for producing a hydrogen product, in which an intermediate product containing water vapor and oxidizable pollutants is formed from a hydrocarbon-containing feedstock and processed to obtain the hydrogen product, wherein water together with oxidizable pollutants is condensed out of the intermediate product to obtain a process condensate (1), from which a deaerator exhaust gas (4) containing water vapor and oxidizable pollutants is removed in a deaerator (D). The invention is characterized in that the deaerator exhaust gas (4) is separated into a water fraction (8) and a gas fraction (7) which is depleted in water vapor and enriched in oxidizable pollutants relative to the deaerator exhaust gas (4), said gas fraction being introduced into the combustion chamber of a process furnace in order to combust the oxidizable pollutants.

Description

[0001] P40370-EP.docx

[0002] November 27, 2024 - Dr. Werner Fischer

[0003] 1

[0004] Description

[0005] Method and device for the disposal of pollutants during hydrogen production

[0006] The invention relates to a process for producing a hydrogen product in which an intermediate product containing water vapor and oxidizable pollutants is formed from a carbon-containing feedstock and processed to the hydrogen product, wherein water together with oxidizable pollutants is condensed from the intermediate product to obtain a process condensate, from which a deaerator exhaust gas containing water vapor and oxidizable pollutants is separated in a deaerator.

[0007] Furthermore, the invention relates to a device for carrying out the method.

[0008] The production of hydrogen products such as pure hydrogen or oxogas from carbon-containing feedstocks has been state of the art for many years. For example, natural gas is converted together with steam in a reforming unit to produce a raw synthesis gas. To convert the hydrocarbons used as completely as possible and to suppress soot formation, the reforming is carried out with an excess of steam, so that the raw synthesis gas contains a significant amount of water in addition to hydrogen and carbon monoxide. In further process steps, the raw synthesis gas is processed into the hydrogen product, whereby water is separated either from the raw synthesis gas or from a gas mixture that is produced from the raw synthesis gas, for example, by a water-gas shift conversion. For water separation, the gas mixture to be treated is cooled to below the steam dew point, causing the steam to condense, and a so-called...Process condensate is formed, consisting predominantly of water and generally contaminated with environmentally harmful substances such as hydrogen, carbon monoxide, methane, methanol, ethanol, formic acid, or acetic acid. If the input contains nitrogen, as is particularly the case with natural gas, which can contain up to 20 mol% nitrogen depending on its origin, significant quantities of ammonia and amines also enter the process condensate. P40370-EP.docx.

[0009] November 27, 2024 - Dr. Werner Fischer

[0010] 2

[0011] According to the prior art, the process condensate is introduced into a degassing device known to those skilled in the art as a deaerator. The deaerator is designed as a stripping column, at the top of which the process condensate is fed. Low-pressure steam is used as the stripping gas, which is introduced via the deaerator sump below the first mass transfer tray or packing and flows upwards from there, with further mass transfer trays or packings providing intensive contact with the countercurrently conveyed process condensate. The stripping gas absorbs the majority of the pollutants contained in the process condensate and, with a water content typically exceeding 95 mol%, is drawn off from the top of the stripping column as deaerator exhaust gas.While the deaerator exhaust gas must be disposed of, process steam for internal use is generated from the purified process condensate that collects in the deaerator sump by evaporation and superheating against process streams that need to be cooled.

[0012] If the pollutant concentrations and quantities in the deaerator exhaust are below the legal limits, it can be released into the atmosphere without further treatment. However, if the concentration of even one pollutant exceeds a legal limit, the deaerator exhaust must be treated appropriately before being released into the atmosphere in order to comply with emissions regulations.

[0013] According to current technology, deaerator exhaust gases are, for example, combusted in a flare with the addition of a fuel gas, or they are completely condensed and then disposed of. All these methods are complex and expensive. Therefore, German patent DE102007059542A1 proposes mixing the deaerator exhaust gas with the oxygen-containing flue gas of a process furnace, where the pollutants combust at temperatures exceeding 600°C. However, the high water content of the deaerator exhaust gas can be problematic, as its high heat capacity cools the flue gas to such an extent that the pollutants are not destroyed, or at least not completely destroyed.

[0014] The object of the invention is to provide a method and a device of the generic type with which the described difficulties in the disposal of deaerator exhaust gas can be overcome. P40370-EP.docx

[0015] November 27, 2024 - Dr. Werner Fischer

[0016] 3

[0017] The problem is solved according to the invention by separating the deaerator exhaust gas into a water fraction and a gas fraction that is depleted of water vapor and enriched with oxidizable pollutants compared to the deaerator exhaust gas, which is introduced into the combustion chamber of a process furnace in order to burn the oxidizable pollutants.

[0018] Process furnaces are defined as steam reformers and fired heaters, which are fired by one or more burners and serve to provide heat required in the process according to the invention itself or in a further process carried out in parallel. The combustion chamber atmosphere of the process furnaces contains free oxygen and has a temperature significantly above 600°C.

[0019] Ideally, the deaerator exhaust gas is cooled below the water dew point to condense the water and concentrate the oxidizable pollutants in the remaining gas fraction. Cooling is best achieved against cooling water and / or air. Alternatively, cold process condensate can be used as a coolant, which must be warmed before being introduced into the deaerator. Typically, process or...

[0020] Low-pressure steam is used, which can be completely or at least partially eliminated by the proposed process variant.

[0021] The two-phase mixture formed during cooling can be introduced into a separator or a stripping column (exhaust gas condensate stripper) to separate the liquid water and gas phases. The resulting gas fraction, which contains the vast majority of the pollutants present in the deaerator exhaust gas, causes only a negligible cooling of the combustion chamber atmosphere when introduced into the process furnace due to its very low water content. Since process furnaces are operated with combustion chamber temperatures well above 600°C and excess oxygen, the oxidizable pollutants are completely combusted.

[0022] Neither the separator nor the exhaust gas condensate stripper produces a completely pollutant-free water fraction from the two-phase mixture (P40370-EP.docx).

[0023] November 27, 2024 - Dr. Werner Fischer

[0024] 4. Rather, the pollutant concentration of the water fraction obtained in the separator is so high that it can neither be used materially – for example, for process steam generation – nor discharged into the environment without undergoing further treatment. A practical variant of the process according to the invention provides for the use of the existing deaerator for treatment, into which the water fraction is fed above the lowest mass transfer plate and preferably at the top, in order to be purified of pollutants together with process condensate.

[0025] Stripping in the exhaust gas condensate stripper, preferably using low-pressure steam as the stripping gas, allows the pollutant concentration of the water fraction to be reduced further than by mere separation. In particular, it is possible to obtain a water fraction from the two-phase mixture that, due to its low pollutant content, is suitable for the production of process steam without further treatment. Advantageously, a water fraction obtained in this way is transferred directly from the sump of the exhaust gas condensate stripper to the deaerator sump and mixed with the process condensate collecting there.

[0026] The inventive recirculation of water contained in the deaerator exhaust gas results in economic advantages in the production of the hydrogen product compared to the prior art, since less fresh water has to be supplied and a smaller amount of wastewater has to be discharged.

[0027] Particularly when the processing of the raw synthesis gas to produce hydrogen includes low-temperature CO conversion, the process condensate can also contain methylamines (mono-, di-, and trimethylamine), which are formed during the conversion from the byproducts ammonia and methanol. These toxic substances, which cause strong odor nuisances even in minute concentrations, enter the water fraction separated from the deaerator exhaust gas due to their high water solubility. They are then returned to the deaerator and thus remain in the process.

[0028] The invention further relates to a device for producing a hydrogen product, comprising a reforming and a processing unit, as described in P40370-EP.docx

[0029] November 27, 2024 - Dr. Werner Fischer

[0030] 5. An intermediate product containing water vapor and oxidizable pollutants is formed from a carbon-containing feedstock and can be processed to the hydrogen product while obtaining a process condensate comprising water and oxidizable pollutants, as well as a deaerator for degassing the process condensate, in which a deaerator exhaust gas containing water vapor and oxidizable pollutants is produced.

[0031] The object stated is solved according to the invention by means of a separation device connected to the combustion chamber of a process furnace, with which the deaerator exhaust gas can be separated into a water fraction and a gas fraction that is depleted of water vapor and enriched with oxidizable pollutants compared to the deaerator exhaust gas for introduction into the combustion chamber of the process furnace.

[0032] Preferably, the separation device includes a heat exchanger in which the deaerator exhaust gas can be cooled below the water dew point in order to condense water and produce a two-phase mixture.

[0033] In one embodiment of the device according to the invention, the separation unit comprises a separator arranged downstream of the heat exchanger, in which the two-phase mixture obtained in the heat exchanger can be separated into the water fraction and the gas fraction, which is depleted of water vapor and enriched with oxidizable pollutants compared to the deaerator exhaust gas. The separator can either be designed as a separate apparatus or integrated into the top of the deaerator.

[0034] In another variant of the device according to the invention, the separation device has an exhaust gas condensate stripper arranged downstream of the heat exchanger, in which the two-phase mixture of substances available in the heat exchanger can be separated by stripping into the water fraction and the gas fraction enriched with water vapor and oxidizable pollutants compared to the exhaust gas.

[0035] A preferred embodiment of the device according to the invention comprises a connecting line between the separation unit and the deaerator, through which the water fraction obtainable in the separation unit can be fed to the head or the sump of the deaerator. P40370-EP.docx

[0036] November 27, 2024 - Dr. Werner Fischer

[0037] 6

[0038] Ideally, the separation device is located above the deaerator, so that the water fraction obtained in the separator or the exhaust gas condensate stripper can be transferred to the deaerator via the connecting pipe using gravity.

[0039] The reforming device of the apparatus according to the invention preferably comprises a burner-fired or electrically heated steam reformer (SMR), an autothermal reformer (ATR), a partial oxidation reactor (POX) or a combination of at least two of these devices, wherein the electrically heated SMR, the ATR and the POX may be assigned a fired heater for heating a feedstock and / or for superheating saturated steam.

[0040] The process furnace, into whose combustion chamber the gas fraction depleted of water vapor and enriched with oxidizable pollutants can be introduced, may belong to a device outside the apparatus according to the invention. Preferably, however, the process furnace is part of the apparatus according to the invention. In particular, the process furnace is a burner-fired steam reformer or a fired heater or auxiliary boiler (auxiliary steam generator) associated with an electrically heated SMR, an ATR, or a POX of the reforming unit.

[0041] The invention will now be explained in more detail with reference to two exemplary embodiments shown schematically in Figures 1 and 2.

[0042] The figures, in which identical plant components and process streams are marked with the same reference symbols, show sections of a process in which an intermediate product containing water vapor and oxidizable pollutants is formed from a hydrocarbon-containing feedstock and processed into a hydrogen product. The resulting process condensate, containing oxidizable pollutants such as hydrogen, carbon monoxide, methane, methanol, ethanol, ammonia, amines, formic acid, or acetic acid, is treated in the process variant shown in Figure 1 using a separator and in the variant shown in Figure 2 using a stripping column.

[0043] To separate pollutants, the process condensate 1, consisting mainly of water, is fed into the head of the deaerator D, from where it is conveyed via P40370-EP.docx

[0044] November 27, 2024 - Dr. Werner Fischer

[0045] 7

[0046] The mass transfer trays flow downwards and are thereby brought into intensive contact with stripping steam 2 supplied via the deaerator sump, which absorbs a large proportion of the pollutants. While the purified process condensate collects in the deaerator sump and is fed to a process steam generator via line 3 (not shown), the separated oxidizable pollutants are drawn off from the top of the deaerator D with the deaerator exhaust gas 4, which consists of up to 95 mol% water, and cooled in the heat exchanger E of the separation unit T against a coolant 5 to below the water dew point.

[0047] The separation device T of Figure 1 comprises a separator A in which the two-phase mixture 6 obtained in the heat exchanger E is separated into a water fraction 8 containing pollutants and a gas fraction 7 that is depleted of water vapor and enriched with oxidizable pollutants compared to the deaerator exhaust gas 4. To further reduce the pollutant content, the water fraction 8 is combined with the process condensate 1 and fed into the top of the deaerator D. Due to its low water content, the gas fraction 7 enriched with oxidizable pollutants can be introduced into the combustion chamber of a process furnace (not shown), where the pollutants are safely combusted at temperatures above 600°C.

[0048] The separation device T' of Figure 2 comprises a stripping column S instead of a separator, in which the two-phase mixture 6 obtained in the heat exchanger E is separated using stripping gas 9. While the gas fraction 7' ​​obtained at the top of the stripping column S, enriched with oxidizable pollutants, is introduced into the combustion chamber of a process furnace (not shown), the water fraction 8' can be fed directly to the bottom of the deaerator D, since it is available with a pollutant content that is significantly lower than that of the water fraction 8.

Claims

P40370-EP.docx November 27, 2024 - Dr. Werner Fischer 8 Patent claims 1. A process for producing a hydrogen product, in which an intermediate containing water vapor and oxidizable pollutants is formed from a hydrocarbon-containing feedstock and processed to produce a hydrogen product, wherein water together with oxidizable pollutants is condensed from the intermediate to obtain a process condensate (1), from which deaerator exhaust gas (4) containing water vapor and oxidizable pollutants is separated in a deaerator (D), characterized in that the deaerator exhaust gas (4) is separated into a water fraction (8, 8') and a gas fraction (7, 7') which is depleted in water vapor and enriched in oxidizable pollutants compared to the deaerator exhaust gas (4), which is introduced into the combustion chamber of a process furnace to combust the oxidizable pollutants.

2. Method according to claim 1, characterized in that the deaerator exhaust gas (4) is cooled to below the water dew point in order to obtain a two-phase mixture (6) which is separated in a separator (A) into the water fraction (8) and the gas fraction (7) which is depleted of water vapor and enriched with oxidizable pollutants compared to the deaerator exhaust gas (4).

3. Method according to claim 2, characterized in that the water fraction (8) obtained in the separator (A) is recycled and fed to the head of the deaerator (D).

4. Method according to claim 1, characterized in that the deaerator exhaust gas (4) is cooled to below the water dew point in order to obtain a two-phase mixture (6) which is fed to a stripping column (S) where it is separated by stripping with steam (9) into the water fraction (8') and the gas fraction (7') which is depleted of water vapor and enriched with oxidizable pollutants compared to the deaerator exhaust gas (4).

5. Method according to claim 4, characterized in that the water fraction (8') obtained by stripping is recycled and introduced into the sump of the deaerator (D). P40370-EP.docx November 27, 2024 - Dr. Werner Fischer 9 6. A method according to any one of claims 1 to 5, characterized in that the hydrocarbon-containing feedstock is subjected to autothermal reforming or steam reforming or partial oxidation or a combination of at least two of these methods to form the intermediate product containing water vapor and oxidizable pollutants.

7. Method according to one of claims 1 to 6, characterized in that the process furnace is used to generate heat required in the method.

8. Device for producing a hydrogen product, comprising a reforming and a processing unit, by which an intermediate product containing water vapor and oxidizable pollutants can be formed from a hydrocarbon-containing feedstock and processed to a hydrogen product while obtaining a process condensate (1) comprising water and oxidizable pollutants, and a deaerator (D) for degassing the process condensate (1), in which deaerator exhaust gas (4) containing water vapor and oxidizable pollutants is produced, characterized in that it comprises a separation device (T, T') connected to the combustion chamber of a process furnace, with which the deaerator exhaust gas (4) can be separated into a water fraction (8, 8') and a gas fraction (7, 7') that is depleted of water vapor and enriched with oxidizable pollutants compared to the deaerator exhaust gas (4) for introduction into the combustion chamber of the process furnace.

9. Device according to claim 8, characterized in that the separation device (T) comprises a heat exchanger (E) in which the deaerator exhaust gas (4) can be cooled to below the water dew point in order to condense water and produce a two-phase mixture (6).

10. Device according to claim 8, characterized in that it has a separator (A) in which the two-phase mixture of substances (6) obtainable in the heat exchanger (E) of the separation device (T) can be separated into the water fraction (8) and the gas fraction (7) which is depleted of water vapor and enriched with oxidizable pollutants compared to the deaerator exhaust gas (4).

11. Device according to claim 8, characterized in that it has a stripping column (S) in which the material in the heat exchanger (E) of the P40370-EP.docx November 27, 2024 - Dr. Werner Fischer 10 The two-phase mixture (6) obtainable by the separation device (T) can be separated by stripping into the water fraction (8') and the gas fraction (7') which is depleted of water vapor and enriched with oxidizable pollutants compared to the deaerator exhaust gas (4).

12. Device according to one of claims 8 to 11, characterized in that the separation device (T) is connected to the deaerator (D) such that the water fraction (8, 8') obtainable in the separation device (T) can be fed to the deaerator (D) either at its top or at the bottom.

13. Device according to one of claims 8 to 12, characterized in that the reforming device comprises a steam reformer or an autothermal reformer or a partial oxidation reactor or a combination of at least two of these devices.

14. Device according to one of claims 8 to 13, characterized in that it comprises the process furnace.

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